CN104420007A - Graphene fiber and preparation method thereof - Google Patents
Graphene fiber and preparation method thereof Download PDFInfo
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- CN104420007A CN104420007A CN201310539358.7A CN201310539358A CN104420007A CN 104420007 A CN104420007 A CN 104420007A CN 201310539358 A CN201310539358 A CN 201310539358A CN 104420007 A CN104420007 A CN 104420007A
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- graphene
- graphene fiber
- fiber
- graphite
- graphite oxide
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- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 title claims abstract description 192
- 229910021389 graphene Inorganic materials 0.000 title claims abstract description 126
- 239000000835 fiber Substances 0.000 title claims abstract description 104
- 238000002360 preparation method Methods 0.000 title claims abstract description 14
- 229910002804 graphite Inorganic materials 0.000 claims abstract description 52
- 239000010439 graphite Substances 0.000 claims abstract description 52
- 230000003647 oxidation Effects 0.000 claims abstract description 12
- 238000007254 oxidation reaction Methods 0.000 claims abstract description 12
- 238000010438 heat treatment Methods 0.000 claims abstract description 11
- 238000001035 drying Methods 0.000 claims abstract description 9
- 239000006185 dispersion Substances 0.000 claims abstract description 7
- 239000000126 substance Substances 0.000 claims abstract description 6
- CSJDCSCTVDEHRN-UHFFFAOYSA-N methane;molecular oxygen Chemical compound C.O=O CSJDCSCTVDEHRN-UHFFFAOYSA-N 0.000 claims abstract description 5
- 238000009987 spinning Methods 0.000 claims abstract description 4
- 239000007864 aqueous solution Substances 0.000 claims description 26
- 238000000034 method Methods 0.000 claims description 21
- 239000000243 solution Substances 0.000 claims description 17
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 claims description 14
- 238000009941 weaving Methods 0.000 claims description 13
- CIWBSHSKHKDKBQ-JLAZNSOCSA-N Ascorbic acid Chemical compound OC[C@H](O)[C@H]1OC(=O)C(O)=C1O CIWBSHSKHKDKBQ-JLAZNSOCSA-N 0.000 claims description 12
- 150000001768 cations Chemical class 0.000 claims description 12
- 239000007787 solid Substances 0.000 claims description 11
- 230000001681 protective effect Effects 0.000 claims description 10
- 230000009467 reduction Effects 0.000 claims description 9
- 238000002347 injection Methods 0.000 claims description 8
- 239000007924 injection Substances 0.000 claims description 8
- -1 polypropylene Polymers 0.000 claims description 8
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 8
- 239000013543 active substance Substances 0.000 claims description 7
- 229910052786 argon Inorganic materials 0.000 claims description 7
- 239000007789 gas Substances 0.000 claims description 7
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 claims description 6
- 239000003795 chemical substances by application Substances 0.000 claims description 6
- KRKNYBCHXYNGOX-UHFFFAOYSA-N citric acid Chemical compound OC(=O)CC(O)(C(O)=O)CC(O)=O KRKNYBCHXYNGOX-UHFFFAOYSA-N 0.000 claims description 6
- 239000007770 graphite material Substances 0.000 claims description 6
- XEEYBQQBJWHFJM-UHFFFAOYSA-N iron Substances [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 claims description 6
- QGZKDVFQNNGYKY-UHFFFAOYSA-O Ammonium Chemical compound [NH4+] QGZKDVFQNNGYKY-UHFFFAOYSA-O 0.000 claims description 5
- 230000002378 acidificating effect Effects 0.000 claims description 5
- 239000002041 carbon nanotube Substances 0.000 claims description 5
- 229910021393 carbon nanotube Inorganic materials 0.000 claims description 5
- 238000001069 Raman spectroscopy Methods 0.000 claims description 4
- 235000010323 ascorbic acid Nutrition 0.000 claims description 4
- 239000011668 ascorbic acid Substances 0.000 claims description 4
- 229960005070 ascorbic acid Drugs 0.000 claims description 4
- 229910052742 iron Inorganic materials 0.000 claims description 4
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims description 3
- 239000004743 Polypropylene Substances 0.000 claims description 3
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical group [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 claims description 3
- 239000002253 acid Substances 0.000 claims description 3
- 230000000694 effects Effects 0.000 claims description 3
- 229910052736 halogen Inorganic materials 0.000 claims description 3
- 239000007788 liquid Substances 0.000 claims description 3
- 238000003801 milling Methods 0.000 claims description 3
- 229920001155 polypropylene Polymers 0.000 claims description 3
- BHPQYMZQTOCNFJ-UHFFFAOYSA-N Calcium cation Chemical compound [Ca+2] BHPQYMZQTOCNFJ-UHFFFAOYSA-N 0.000 claims description 2
- JPVYNHNXODAKFH-UHFFFAOYSA-N Cu2+ Chemical compound [Cu+2] JPVYNHNXODAKFH-UHFFFAOYSA-N 0.000 claims description 2
- JLVVSXFLKOJNIY-UHFFFAOYSA-N Magnesium ion Chemical compound [Mg+2] JLVVSXFLKOJNIY-UHFFFAOYSA-N 0.000 claims description 2
- NPYPAHLBTDXSSS-UHFFFAOYSA-N Potassium ion Chemical compound [K+] NPYPAHLBTDXSSS-UHFFFAOYSA-N 0.000 claims description 2
- FKNQFGJONOIPTF-UHFFFAOYSA-N Sodium cation Chemical compound [Na+] FKNQFGJONOIPTF-UHFFFAOYSA-N 0.000 claims description 2
- PTFCDOFLOPIGGS-UHFFFAOYSA-N Zinc dication Chemical compound [Zn+2] PTFCDOFLOPIGGS-UHFFFAOYSA-N 0.000 claims description 2
- 235000011054 acetic acid Nutrition 0.000 claims description 2
- 229910001424 calcium ion Inorganic materials 0.000 claims description 2
- 235000015165 citric acid Nutrition 0.000 claims description 2
- 229910001431 copper ion Inorganic materials 0.000 claims description 2
- DDXLVDQZPFLQMZ-UHFFFAOYSA-M dodecyl(trimethyl)azanium;chloride Chemical compound [Cl-].CCCCCCCCCCCC[N+](C)(C)C DDXLVDQZPFLQMZ-UHFFFAOYSA-M 0.000 claims description 2
- 239000003814 drug Substances 0.000 claims description 2
- 229940079593 drug Drugs 0.000 claims description 2
- 238000005189 flocculation Methods 0.000 claims description 2
- 230000016615 flocculation Effects 0.000 claims description 2
- 239000001307 helium Substances 0.000 claims description 2
- 229910052734 helium Inorganic materials 0.000 claims description 2
- SWQJXJOGLNCZEY-UHFFFAOYSA-N helium atom Chemical compound [He] SWQJXJOGLNCZEY-UHFFFAOYSA-N 0.000 claims description 2
- 229910001425 magnesium ion Inorganic materials 0.000 claims description 2
- 125000004433 nitrogen atom Chemical group N* 0.000 claims description 2
- 125000004437 phosphorous atom Chemical group 0.000 claims description 2
- 150000008442 polyphenolic compounds Chemical class 0.000 claims description 2
- 235000013824 polyphenols Nutrition 0.000 claims description 2
- 229910001414 potassium ion Inorganic materials 0.000 claims description 2
- 230000008569 process Effects 0.000 claims description 2
- 229910001415 sodium ion Inorganic materials 0.000 claims description 2
- CPELXLSAUQHCOX-UHFFFAOYSA-N Hydrogen bromide Chemical compound Br CPELXLSAUQHCOX-UHFFFAOYSA-N 0.000 claims 2
- 229910000042 hydrogen bromide Inorganic materials 0.000 claims 1
- XMBWDFGMSWQBCA-UHFFFAOYSA-N hydrogen iodide Chemical compound I XMBWDFGMSWQBCA-UHFFFAOYSA-N 0.000 claims 1
- 229910000043 hydrogen iodide Inorganic materials 0.000 claims 1
- 229910052757 nitrogen Inorganic materials 0.000 claims 1
- 238000004132 cross linking Methods 0.000 abstract description 2
- 229920000049 Carbon (fiber) Polymers 0.000 description 6
- 229910052799 carbon Inorganic materials 0.000 description 6
- 239000004917 carbon fiber Substances 0.000 description 6
- 230000001112 coagulating effect Effects 0.000 description 5
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 description 5
- 238000010792 warming Methods 0.000 description 5
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 4
- 239000000463 material Substances 0.000 description 4
- 229910052760 oxygen Inorganic materials 0.000 description 4
- 239000013078 crystal Substances 0.000 description 3
- 239000008367 deionised water Substances 0.000 description 3
- 229910021641 deionized water Inorganic materials 0.000 description 3
- 239000001301 oxygen Substances 0.000 description 3
- ZZZCUOFIHGPKAK-UHFFFAOYSA-N D-erythro-ascorbic acid Natural products OCC1OC(=O)C(O)=C1O ZZZCUOFIHGPKAK-UHFFFAOYSA-N 0.000 description 2
- 229910000831 Steel Inorganic materials 0.000 description 2
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 2
- 229930003268 Vitamin C Natural products 0.000 description 2
- 238000013019 agitation Methods 0.000 description 2
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 2
- 239000002134 carbon nanofiber Substances 0.000 description 2
- 231100000045 chemical toxicity Toxicity 0.000 description 2
- 239000002131 composite material Substances 0.000 description 2
- 230000005611 electricity Effects 0.000 description 2
- 239000002657 fibrous material Substances 0.000 description 2
- 125000000524 functional group Chemical group 0.000 description 2
- 238000004519 manufacturing process Methods 0.000 description 2
- 229910052751 metal Inorganic materials 0.000 description 2
- 239000002184 metal Substances 0.000 description 2
- 239000000843 powder Substances 0.000 description 2
- 239000002243 precursor Substances 0.000 description 2
- 238000012545 processing Methods 0.000 description 2
- 238000012797 qualification Methods 0.000 description 2
- 239000010959 steel Substances 0.000 description 2
- 235000019154 vitamin C Nutrition 0.000 description 2
- 239000011718 vitamin C Substances 0.000 description 2
- UXVMQQNJUSDDNG-UHFFFAOYSA-L Calcium chloride Chemical compound [Cl-].[Cl-].[Ca+2] UXVMQQNJUSDDNG-UHFFFAOYSA-L 0.000 description 1
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 1
- MHAJPDPJQMAIIY-UHFFFAOYSA-N Hydrogen peroxide Chemical compound OO MHAJPDPJQMAIIY-UHFFFAOYSA-N 0.000 description 1
- 239000004952 Polyamide Substances 0.000 description 1
- 238000001237 Raman spectrum Methods 0.000 description 1
- BQCADISMDOOEFD-UHFFFAOYSA-N Silver Chemical compound [Ag] BQCADISMDOOEFD-UHFFFAOYSA-N 0.000 description 1
- 229910021383 artificial graphite Inorganic materials 0.000 description 1
- 230000001174 ascending effect Effects 0.000 description 1
- 239000001110 calcium chloride Substances 0.000 description 1
- 229910001628 calcium chloride Inorganic materials 0.000 description 1
- 150000001721 carbon Chemical group 0.000 description 1
- 239000003575 carbonaceous material Substances 0.000 description 1
- 238000003763 carbonization Methods 0.000 description 1
- 230000008859 change Effects 0.000 description 1
- 238000006243 chemical reaction Methods 0.000 description 1
- 238000005229 chemical vapour deposition Methods 0.000 description 1
- 238000005660 chlorination reaction Methods 0.000 description 1
- 238000004140 cleaning Methods 0.000 description 1
- 238000011284 combination treatment Methods 0.000 description 1
- 238000001816 cooling Methods 0.000 description 1
- 229910052802 copper Inorganic materials 0.000 description 1
- 239000010949 copper Substances 0.000 description 1
- 229910000365 copper sulfate Inorganic materials 0.000 description 1
- ARUVKPQLZAKDPS-UHFFFAOYSA-L copper(II) sulfate Chemical compound [Cu+2].[O-][S+2]([O-])([O-])[O-] ARUVKPQLZAKDPS-UHFFFAOYSA-L 0.000 description 1
- 238000000354 decomposition reaction Methods 0.000 description 1
- 230000007123 defense Effects 0.000 description 1
- 238000000151 deposition Methods 0.000 description 1
- 230000008021 deposition Effects 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 238000005530 etching Methods 0.000 description 1
- 238000002474 experimental method Methods 0.000 description 1
- 238000001914 filtration Methods 0.000 description 1
- 230000008676 import Effects 0.000 description 1
- 239000004973 liquid crystal related substance Substances 0.000 description 1
- 230000007246 mechanism Effects 0.000 description 1
- 239000011325 microbead Substances 0.000 description 1
- 239000011259 mixed solution Substances 0.000 description 1
- 239000000203 mixture Substances 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- DOTMOQHOJINYBL-UHFFFAOYSA-N molecular nitrogen;molecular oxygen Chemical compound N#N.O=O DOTMOQHOJINYBL-UHFFFAOYSA-N 0.000 description 1
- 229920002239 polyacrylonitrile Polymers 0.000 description 1
- 229920002647 polyamide Polymers 0.000 description 1
- 229920000098 polyolefin Polymers 0.000 description 1
- 239000012286 potassium permanganate Substances 0.000 description 1
- 238000010248 power generation Methods 0.000 description 1
- 230000004044 response Effects 0.000 description 1
- 229910052709 silver Inorganic materials 0.000 description 1
- 239000004332 silver Substances 0.000 description 1
- 238000005245 sintering Methods 0.000 description 1
- 230000003068 static effect Effects 0.000 description 1
- 238000003756 stirring Methods 0.000 description 1
- 239000000758 substrate Substances 0.000 description 1
- 238000006277 sulfonation reaction Methods 0.000 description 1
- 229910052717 sulfur Inorganic materials 0.000 description 1
- 239000011593 sulfur Substances 0.000 description 1
- 230000008961 swelling Effects 0.000 description 1
- 238000012360 testing method Methods 0.000 description 1
- 231100000419 toxicity Toxicity 0.000 description 1
- 230000001988 toxicity Effects 0.000 description 1
- 238000007740 vapor deposition Methods 0.000 description 1
- 230000010148 water-pollination Effects 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
- C01B32/00—Carbon; Compounds thereof
- C01B32/15—Nano-sized carbon materials
- C01B32/182—Graphene
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
- C01B32/00—Carbon; Compounds thereof
- C01B32/15—Nano-sized carbon materials
- C01B32/182—Graphene
- C01B32/198—Graphene oxide
-
- D—TEXTILES; PAPER
- D01—NATURAL OR MAN-MADE THREADS OR FIBRES; SPINNING
- D01D—MECHANICAL METHODS OR APPARATUS IN THE MANUFACTURE OF ARTIFICIAL FILAMENTS, THREADS, FIBRES, BRISTLES OR RIBBONS
- D01D5/00—Formation of filaments, threads, or the like
- D01D5/06—Wet spinning methods
-
- D—TEXTILES; PAPER
- D01—NATURAL OR MAN-MADE THREADS OR FIBRES; SPINNING
- D01F—CHEMICAL FEATURES IN THE MANUFACTURE OF ARTIFICIAL FILAMENTS, THREADS, FIBRES, BRISTLES OR RIBBONS; APPARATUS SPECIALLY ADAPTED FOR THE MANUFACTURE OF CARBON FILAMENTS
- D01F9/00—Artificial filaments or the like of other substances; Manufacture thereof; Apparatus specially adapted for the manufacture of carbon filaments
- D01F9/08—Artificial filaments or the like of other substances; Manufacture thereof; Apparatus specially adapted for the manufacture of carbon filaments of inorganic material
- D01F9/12—Carbon filaments; Apparatus specially adapted for the manufacture thereof
-
- D—TEXTILES; PAPER
- D01—NATURAL OR MAN-MADE THREADS OR FIBRES; SPINNING
- D01D—MECHANICAL METHODS OR APPARATUS IN THE MANUFACTURE OF ARTIFICIAL FILAMENTS, THREADS, FIBRES, BRISTLES OR RIBBONS
- D01D5/00—Formation of filaments, threads, or the like
- D01D5/0007—Electro-spinning
- D01D5/0015—Electro-spinning characterised by the initial state of the material
- D01D5/003—Electro-spinning characterised by the initial state of the material the material being a polymer solution or dispersion
- D01D5/0046—Electro-spinning characterised by the initial state of the material the material being a polymer solution or dispersion the fibre formed by coagulation, i.e. wet electro-spinning
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y10—TECHNICAL SUBJECTS COVERED BY FORMER USPC
- Y10T—TECHNICAL SUBJECTS COVERED BY FORMER US CLASSIFICATION
- Y10T428/00—Stock material or miscellaneous articles
- Y10T428/29—Coated or structually defined flake, particle, cell, strand, strand portion, rod, filament, macroscopic fiber or mass thereof
- Y10T428/2913—Rod, strand, filament or fiber
- Y10T428/2918—Rod, strand, filament or fiber including free carbon or carbide or therewith [not as steel]
Landscapes
- Chemical & Material Sciences (AREA)
- Engineering & Computer Science (AREA)
- Organic Chemistry (AREA)
- Materials Engineering (AREA)
- Nanotechnology (AREA)
- Inorganic Chemistry (AREA)
- Textile Engineering (AREA)
- Mechanical Engineering (AREA)
- Chemical Kinetics & Catalysis (AREA)
- General Chemical & Material Sciences (AREA)
- Inorganic Fibers (AREA)
- Carbon And Carbon Compounds (AREA)
Abstract
The invention provides a graphene fiber and a preparation method thereof, the graphene fiber is formed by a graphite oxidation step, a dispersion step, a spinning step, a drying step and a heat treatment step, the diameter of the graphene fiber is less than 100 mu m, the length-diameter ratio of the graphene fiber is more than 10, and the carbon-oxygen element ratio of the graphene fiber is more than 5; the graphene fiber is formed by mutually cross-linking and stacking a plurality of graphene sheets in an axial mode, wherein the thickness of the graphene sheets is less than 3nm, and the graphene sheets are tightly connected through chemical bonding, so that the graphene fiber has excellent mechanical properties and electric/heat conduction characteristics.
Description
Technical field
The present invention relates to a kind of graphene fiber, and the preparation method of this graphene fiber.
Background technology
Carbon fiber is a kind of fibrous material having chemical inertness and semiconducting behavior concurrently, has the excellent properties such as lightweight, intensity is high, modulus of elasticity is high.High performance fibrous carbon material is not only widely used in space flight and aviation, national defense and military industry at present, and also there is wide application space on automobile industry and wind power generation blade, nuclear power, outdoor activity product.European patent case EP1696046B1 discloses one and utilizes pulse electric current sintering legal system for metal carbon fibre composite, and this composite has the cooling mechanism that splendid thermal conductivity can be applicable to electronic equipment or power module.It take polyamide fiber as the method that precursor prepares carbon fiber that United States Patent (USP) case US2013/0084455A1 then discloses a kind of, and this case utilizes polyolefin precursor sulfonation degree to control, the characteristic of carbon fiber finished product and morphology of carbon fibers after adjustable carbonization.
Graphene is with the two dimensional crystal of sp2 hybridized orbital composition hexagonal honeycomb arrangement, thickness 0.335nm, only a carbon atom diameter, it is material the thinnest in the world at present, but have outstanding mechanical property, mechanical strength far above iron and steel hundred times, proportion but only about iron and steel 1/4th; And electrical properties part, resistance comparatively copper and silver low, in current known materials under room temperature resistance minimum, and electron mobility is high, and being therefore applied to materials of electronic components has outstanding performance; Its a few near-transparent adds to possess satisfactory electrical conductivity, also receives publicity on photoelectric field.United States Patent (USP) case US2012/0298396A1 discloses a kind of graphene fiber preparation method, utilizes chemical vapour deposition technique to be deposited on by Graphene on a line style metal substrate, then is soaked in etching solution and obtains graphene fiber.Aforementioned carried Patent Case is a kind of ascending method preparing graphene fiber, but its shortcoming to be deposition velocity slow and need to utilize the material of the certain toxicity of tool in CVD processing procedure.
Summary of the invention
Main purpose of the present invention is to provide a kind of graphene fiber, the diameter of this graphene fiber is less than 100 μm, and draw ratio is greater than 10, goodly be greater than 500, this graphene fiber and general vapor deposition carbon fiber (Vapor Grown Carbon Fiber, VGCF), or the maximum difference of the carbon fiber of polyacrylonitrile high temperature cabonization is, graphene fiber comprises multiple graphene film, and the in-plane of described multiple graphene film is all parallel to the axis of these graphene fibers, wherein the thickness of graphene film is less than 3nm, and it is tightly connected with chemical bonded refractory between each graphene film, therefore this graphene fiber has excellent engineering properties, TENSILE STRENGTH is greater than 100MPa, and young's modulus is greater than 1GPa.
This graphene fiber has excellent heat conduction and conduction property more simultaneously, and electrical conductivity is 10
-2to 10
3s/cm, and heat-conduction value is greater than 10W/mK.
Another object of the present invention is to provide a kind of preparation method of graphene fiber, and the method comprises graphite oxidation step, dispersion steps, weaving step, drying steps and heat treatment step.Graphite oxidation step is oxidized by graphite material, forms graphite oxide; Dispersion steps is scattered in water by graphite oxide, forms the graphite oxide aqueous solution, because of the STRUCTURE DECOMPOSITION that graphite oxide is loose, and formed multiple with the graphene film determining axially-aligned.Weaving step is utilized by the graphite oxide aqueous solution method of weaving to inject one second solution, the graphite oxide aqueous solution contacted with the second solution, and forms the graphene fiber of prereduction.Drying steps is separated with the aqueous solution by the graphene fiber of prereduction and carries out drying.Heat treatment step is in the protective atmosphere with heat treatment temperature, and the graphene fiber of prereduction is carried out thermal reduction, forms a graphene fiber.
The graphene fiber that the present invention obtains, there is good intensity, conduct electricity hot, and preparation method directly can import conventional weaving method obtains graphene fiber material, processing procedure is comparatively simple, the environment of integral manufacturing significantly can reduce chemical toxicity simultaneously, promote overall security, and time and the cost of making can be reduced significantly.
Accompanying drawing explanation
Fig. 1 is the structural representation of graphene fiber of the present invention;
Fig. 2 is preparation method's flow chart of graphene fiber of the present invention; And
Fig. 3 shows the present invention measures each experimental example result with Raman spectrometer.
Wherein, description of reference numerals is as follows:
1 graphene fiber
10 graphene films
The preparation method of S1 graphene fiber
S10 graphite oxidation step
S20 dispersion steps
S30 weaves step
S40 drying steps
S50 heat treatment step
Detailed description of the invention
Below coordinate graphic and component symbol to do more detailed description to embodiments of the present invention, can implement according to this with reference to description word to make those skilled in the art.
Consulting Fig. 1, is the structural representation of graphene fiber of the present invention.As shown in Figure 1, graphene fiber 1 of the present invention comprises multiple graphene oxide sheet 10, the thickness of described graphene film 10 is less than 3nm, and be cross-linked with each other stacking around an axial A, wherein the diameter D of this graphene fiber 1 is less than 100 μm, length H is greater than 10 with diameter D ratio (H/D), and the carbon oxygen element ratio of this graphene fiber is greater than 5 after measured.
Consulting Fig. 2, is preparation method's flow chart of graphene fiber of the present invention.As shown in Figure 2, the preparation method S1 of graphene fiber of the present invention comprises graphite oxidation step S10, dispersion steps S20, weaving step S30, drying steps S40 and heat treatment step S50.
One graphite material oxidation is formed graphite oxide by graphite oxidation step S10, graphite material can be selected from native graphite (graphite), expanded graphite (expanded graphite), electrographite (artificial graphite), graphite fibre (graphite fiber), CNT (carbon nano-tube) (carbon nano-tube) and carbonaceous mesophase spherules (mesophase carbon micro-bead) at least one of them, the mode of oxidation is Han Mosi (Hummers) method, but is not limited thereto.After oxidation step S10, a large amount of oxycarbide functional groups can be formed, as C-O and C=O etc., make graphite material oxygen content significantly rise and form structure comparatively swelling and loose graphite oxide.
Dispersion steps S20, described graphite oxide is scattered in water, and form a graphite oxide aqueous solution, the concentration of graphite oxide is 1-10mg/mL, and graphite oxide is in this graphite oxide aqueous solution, loose destructing is decomposed, formed with multiple graphene oxide sheets of the parallel assortment of a long axis direction, the thickness of this graphene oxide sheet is less than 3nm, because the functional group on graphite oxide surface can dissociate, during graphene oxide sheet in the graphite oxide aqueous solution, surface is with a large amount of negative electrical charge, make to produce repulsion between graphene oxide sheet, form a uniform graphite oxide aqueous solution, simultaneously in this concentration range, graphene oxide sheet can be made to present nematic crystal (nematic liguid crystal) character, and there is the regularly arranged of one degree of freedom.
This graphite oxide aqueous solution is injected one second solution with liquid drugs injection spinning or electrical spinning method by weaving step S30, this graphene oxide sheet is contacted at this second solution, the at least 0.5 hour time of contact, this second solution at least includes at least one cation interfacial active agent, at least one CATION and at least one acidic reduction agent, make to produce chemical bonded refractory between oxidized graphite flake, and be reduced into prereduction graphene fiber.
Because the graphite oxide aqueous solution is liquid crystal arrangement, when it is subject to driving force extruding injection second solution, this graphene oxide sheet all moves arrangement with the direction being parallel to driving force, and containing cation interfacial active agent and CATION in second aqueous solution, when the graphite oxide aqueous solution injects the second solution, positive charge can be combined with the negative electrical charge on graphene oxide sheet surface rapidly, carry out cross-linking reaction, make to produce chemical bonded refractory between graphene oxide sheet, form the effect of flocculation, and form graphene oxide fiber, again by acidic reduction agent further by graphene oxide fiber reduction, reduce its hydrophily, and form prereduction graphene fiber.
This cation interfacial active agent has two ends, the one end at these two ends has a Long carbon chain lipophilic group, wherein the other end has the hydrophilic radical of at least one nitrogen-atoms, sulphur atom or phosphorus atoms, therefore this hydrophilic radical is with the interfacial agent of positive charge, further, this cation interfacial active agent can be selected from any one or its combination of softex kw, polypropylene milling ammonium or Dodecyl trimethyl ammonium chloride.This CATION is selected from any one or its combination of potassium ion, sodium ion, copper ion, calcium ion, zinc ion, magnesium ion, iron ion or ammonium ion, and this acidic reduction agent is selected from any one or its combination of ascorbic acid, citric acid, polyphenol, acetic acid and halogen acids.
Prereduction graphene fiber takes out by drying steps S40 in the second solution, and makes the fully drying of moisture, organic solution, volatilization, obtains prereduction graphene fiber solid.
The prereduction graphene fiber solid of prereduction is positioned in protective atmosphere and heat-treats by heat treatment step S50, and prereduction graphene fiber solid is fully reduced, and strengthens the bond intensity between graphene film simultaneously, and obtains graphene fiber.
At this, protective atmosphere is helium (He), argon gas (Ar) and nitrogen (N
2) any one or its combination, and heat treatment temperature be best with 300-1500 DEG C, and heat treatment time was the best with 10-120 minute.
Through qualification, the final carbon oxygen element ratio of this graphene fiber (C/O than) is greater than 5, when via Raman spectrum qualification structure, and its I
d/ I
gsignal ratio be 0.5 ~ 1.5, and I
2D/ I
gsignal ratio be 0.1 ~ 1.2.
Following experimental example 1-5 illustrates graphene fiber of the present invention and knits preparation method, and wherein graphite oxidation carries out with Han Mosifa, gets the sulfuric acid (H that graphite powder 10g is placed in 230ml
2sO
4) in, in ice bath, slowly add 30g potassium permanganate (KMnO
4) Keep agitation, in process, solution is maintained at less than 20 DEG C, after completing at 35 DEG C Keep agitation at least 40 minutes, slowly add the deionized water of 460ml again in mixed solution, bath temperature 35 DEG C is kept to continue to stir at least 20 minutes, after question response terminates, by 1.4L deionized water and 100ml hydrogen peroxide (H
2o
2) add in solution, static placement 24 hours, finally dry with 5% hydrochloric acid (HC1) cleaning and filtering and in vacuum environment, and obtain graphite oxidation powder, again this powder is added in deionized water and be configured to concentration 10mg/mL, and the uniform graphite oxide aqueous solution.
< experimental example 1>
The graphite oxide aqueous solution getting above-mentioned concentration 10g/mL adopts wet type weaving, the softex kw aqueous solution of injection 25 DEG C of concentration 0.5mg/ml is extruded with the speed of 10ml/min, stop 60min and form graphene oxide fiber to solidify, graphene oxide fiber is filtered taking-up in coagulating bath, its moisture content dry under room temperature, obtain graphene oxide fibre solid, finally graphene oxide fiber is positioned in protective atmosphere argon gas (Ar) and heat-treats, be warming up to 1500 DEG C with 3 DEG C/min speed and hold temperature 2 hours, obtain graphene fiber.
< experimental example 2>
The graphite oxide aqueous solution getting above-mentioned concentration 10mg/mL adopts wet type weaving, extrudes the softex kw aqueous solution of injection 25 DEG C of concentration 0.5mg/ml with the speed of 10ml/min, stops 60min to solidify graphene oxide fiber.Add the aqueous ascorbic acid that 100ml concentration is 10mg/ml again, be placed in 90 DEG C of baking ovens and form prereduction graphene fiber in 4 hours, again prereduction graphene fiber is filtered taking-up in coagulating bath, its moisture content dry under room temperature, prereduction graphene fiber solid.Finally prereduction graphene fiber solid is positioned in protective atmosphere argon gas (Ar) and heat-treats, be warming up to 1500 DEG C with 3 DEG C/min speed and hold temperature 2 hours, obtain graphene fiber.
< experimental example 3>
The graphite oxide aqueous solution getting above-mentioned concentration 10mg/mL adopts wet type weaving, extrude with the speed of 10ml/min the Vitamin C aqueous solution that the polypropylene milling ammonium of injection 25 DEG C of concentration 0.5mg/ml and concentration are 2.5mg/ml, stop 4 hours to solidify and to form prereduction graphene fiber.Again prereduction graphene fiber is filtered taking-up in coagulating bath, under room temperature, its moisture content dry, obtains prereduction graphene fiber solid.Finally prereduction graphene fiber is positioned in protective atmosphere argon gas (Ar) and heat-treats, be warming up to 1500 DEG C with 3 DEG C/min speed and hold temperature 2 hours, obtain graphene fiber.
< experimental example 4>
The graphite oxide aqueous solution getting above-mentioned concentration 10mg/mL adopts wet type weaving, extrudes the copper sulfate solution of injection 25 DEG C of concentration 5wt% with the speed of 10ml/min, stops 30min and solidifies graphene oxide fiber.Again graphene oxide fiber is filtered taking-up in coagulating bath, at 50 DEG C, dry its moisture content, obtain graphene oxide fibre solid.Graphene oxide fibre solid being soaked in the aqueous ascorbic acid that concentration is 2.5mg/ml, being statically placed in 90 DEG C of baking ovens 6 hours, is prereduction graphene fiber by graphene oxide fiber reduction.Finally prereduction graphene fiber is positioned in protective atmosphere argon gas (Ar) and heat-treats, be warming up to 1500 DEG C with 3 DEG C/min speed and hold temperature 2 hours, obtain tool graphene fiber.
< experimental example 5>
The graphite oxide aqueous solution getting above-mentioned concentration 10mg/mL adopts wet type weaving, extrude injection 25 DEG C of concentration with the speed of 10ml/min and be respectively the softex kw of 0.5mg/ml, 5wt% calcium chloride and 2.5mg/ml Vitamin C mixed water solution, stop 4 hours to solidify and to form the graphene fiber of prereduction.Again the graphene fiber of prereduction is filtered taking-up in coagulating bath; under room temperature after its moisture content dry; finally graphene oxide fiber is positioned in protective atmosphere argon gas (Ar) and heat-treats; be warming up to 1500 DEG C with 3 DEG C/min speed and hold temperature 2 hours, obtain tool graphene fiber.
Test after experiment, the electrical conductivity of the graphene fiber that experimental example 1-5 obtains is 10
-2to 10
3s/cm, the coefficient of heat conduction is 90 ~ 1000W/mK TENSILE STRENGTH is 100 ~ 1000MPa; And young's modulus is the graphene fiber of 1 ~ 10GPa, draw ratio is greater than 10, is goodly greater than 500; Utilized by this graphene fiber nitrogen oxygen analyzer and carbon and sulfur analytical instrument to analyze the content of carbon and oxygen, the carbon-to-oxygen ratio that can obtain this graphene fiber is greater than 5, is preferably 15 ~ 60.
Fig. 3 shows the present invention measures each experimental example result with Raman spectrometer.As shown in Figure 3, Raman spectrometer is measured, and shows this fiber and is made up of graphene-structured, intensity (I
d/ I
g) be the ratio (I of 0.5 ~ 1.5, Gband intensity
2D/ I
gbe 0.1 ~ 0.2).
The graphene fiber that the present invention obtains, has good intensity, conducts electricity hot, only also originally completed with aqueous solution chlorination simultaneously, preparation method is comparatively simple, the environment of integral manufacturing significantly can reduce chemical toxicity, promotes overall security, and can reduce time and the cost of making significantly.
As described above is only to explain preferred embodiment of the present invention; not attempt does any pro forma restriction to the present invention according to this; therefore, all have any modification for the present invention or the change done under identical invention spirit, all must be included in the category that the invention is intended to protect.
Claims (11)
1. a graphene fiber, is characterized in that, comprises:
Multiple graphene film, described graphene film is cross-linked with each other stacking around an axial manner, and the thickness of wherein said graphene film is less than 3nm.
2. graphene fiber as claimed in claim 1, it is characterized in that, the diameter of this graphene fiber is less than 100 μm, and draw ratio is greater than 10, and the carbon oxygen element ratio of this graphene fiber is greater than 5.
3. graphene fiber as claimed in claim 1, it is characterized in that, the electrical conductivity of this graphene fiber is 10
-2to 10
3s/cm, the coefficient of heat conduction are 90 ~ 1000W/mK, TENSILE STRENGTH is 100 ~ 1000MPa and young's modulus is the graphene fiber of 1 ~ 10GPa; Measure with Raman spectrometer, show this fiber and be made up of graphene-structured, intensity (I
d/ I
g) be the ratio (I of 0.5 ~ 1.5, G band intensity
2D/ I
gbe 0.1 ~ 1.2).
4. a preparation method for graphene fiber, is characterized in that, comprises following steps:
One graphite oxidation step, is oxidized a graphite material, and forms multiple graphite oxide;
One dispersion steps, be scattered in water by described graphite oxide, and form a graphite oxide aqueous solution, the concentration of described graphite oxide is 1-10mg/mL, and described graphite oxide is in this graphite oxide aqueous solution, be formed with multiple graphene oxide sheets of the parallel assortment of a long axis direction;
One weaving step, this graphite oxide aqueous solution is injected one second solution with weaving techniques, this graphite oxide aqueous solution is contacted with this second solution, to carry out a liquid drugs injection spin processes or an electrical spinning method, at least 0.5 hour this contact time, this second liquid includes at least one cation interfacial active agent, at least one CATION and at least one acidic reduction agent, make to produce chemical bonded refractory between described graphene oxide sheet, form the effect of flocculation, and a prereduction graphene fiber is formed in this second solution, and the plane of this graphene film is all parallel to the axis of fiber,
One drying steps, this prereduction graphene fiber is dry, and form a prereduction graphene fiber solid;
One reduction step, heat-treats this prereduction graphene fiber solid, and obtains a graphene fiber in a protective atmosphere,
The diameter of this wherein obtained graphene fiber is less than 100 μm, and draw ratio is greater than 10, and the carbon oxygen element ratio of this graphene fiber is greater than 5.
5. method as claimed in claim 4, is characterized in that, this graphite material be selected from native graphite, expanded graphite, electrographite, graphite fibre, CNT (carbon nano-tube) and carbonaceous mesophase spherules at least one of them.
6. method as claimed in claim 4, it is characterized in that, this cation interfacial active agent has two ends, and the one end at these two ends has a Long carbon chain lipophilic group, and wherein the other end has the hydrophilic radical of at least one nitrogen-atoms, sulphur atom or phosphorus atoms.
7. method as claimed in claim 4, is characterized in that, this cation interfacial active agent is selected from any one or its combination of softex kw, polypropylene milling ammonium or Dodecyl trimethyl ammonium chloride.
8. method as claimed in claim 4, is characterized in that, this CATION is selected from any one or its combination of potassium ion, sodium ion, copper ion, calcium ion, zinc ion, magnesium ion, iron ion or ammonium ion.
9. method as claimed in claim 4, is characterized in that, this acidic reduction agent is selected from any one or its combination of ascorbic acid, citric acid, polyphenol, acetic acid and halogen acids.
10. method as claimed in claim 9, wherein this halogen acids is selected from any one or its combination of hydrogen iodide and hydrogen bromide.
11. methods as claimed in claim 4, is characterized in that, this heat treatment temperature is the scope of 300-1500 DEG C, and a heat treatment time was the scope of 10-120 minute, and this heat treated protective atmosphere is selected from any one or its combination of helium, argon gas and nitrogen.
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| TW102131586A TWI546431B (en) | 2013-09-02 | 2013-09-02 | Graphene fiber and its preparation method |
| TW102131586 | 2013-09-02 |
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| US (1) | US20150064463A1 (en) |
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Also Published As
| Publication number | Publication date |
|---|---|
| TWI546431B (en) | 2016-08-21 |
| US20150064463A1 (en) | 2015-03-05 |
| CN104420007B (en) | 2016-11-02 |
| TW201510298A (en) | 2015-03-16 |
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Address after: 100085 Building 301-16, No. 1 Hospital, Gaolizhang Road, Haidian District, Beijing Patentee after: Beijing Ensemble Technology Co., Ltd. (Limited Partnership) Address before: 11th Floor, Block A, 8 Xueqing Road, Haidian District, Beijing, 100192 Patentee before: Beijing science and Technology Co., Ltd. |